O-Alkyl-S-n-propyl-N-sulfonyl-phosphoric acid ester amides

ABSTRACT

O-Alkyl-S-n-propyl-N-sulfonyl-phosphoric acid ester amides of the formula ##STR1## in which R 1  is methyl or ethyl, 
     R 2  is C 1  -C 6  alkyl or alkenyl, C 1  -C 6  alkyl substituted by aryl, phenyl, C 1  -C 6  alkylphenyl, or halophenyl 
     R 3  is C 1  -C 6  alkyl, C 1  -C 6  alkyl substituted by halogen, phenyl, C 1  -C 6  alkylphenyl, C 1  -C 6  alkoxyphenyl, halophenyl, or nitrophenyl, and 
     X is oxygen or sulfur, 
     Which possess insecticidal, acaricidal and nematicidal properties.

The present invention relates to and has for its objects the provisionof particular new O-alkyl-S-n-propyl-N-sulfonylphosphoric acid esteramides, which possess insecticidal, acaricidal and nematicidalproperties, active compositions in the form of mixtures of suchcompounds with solid and liquid dispersible carrier vehicles, andmethods for producing such compounds and for using such compounds in anew way especially for combating pests, e.g. insects, acarids andnematodes, with other and further objects becoming apparent from a studyof the within specification and accompanying examples.

U.S. Pat. No. 3,716,600 discloses that a wide variety of compounds ofthe general formula ##STR2## in which

R represents an alkyl group having 1 to 3 carbon atoms,

R' represents an aliphatic group having 1 to 3 carbon atoms,

R" represents an alkyl group having 1 to 10 carbon atoms, a cycloalkylgroup having 3 to 8 carbon atoms or a phenyl group, and

Y represents an oxygen or sulfur atom,

Have insecticidal and acaricidal activities.

Hitherto, parathion has been widely used as an insecticide, for examplefor controlling rice borers, planthoppers and leafhoppers which areimportant insects that are harmful to rice. The use of parathion,however, has been suspended in some areas, particularly in Japan,because despite its excellent effectiveness against the pests, there isconsidered to be a great danger of its causing acute toxicity tomammals.

Furthermore, the long-term use of large amounts of organophosphoruscompounds, such as parathion, EPN, BAYCID and Sumithion, organochlorinecompounds, such as BHC and DDT, and carbamate compounds, such as Sevin,is bringing about the deplorable phenomenon that the pests aredeveloping resistance to these chemicals.

Hence there is a need for new pesticides which have only a low toxicityto warm-blooded animals but which are effective against those pests thathave attained resistance to prior-art pesticides.

The present invention provides phosphoric acid ester amides of thegeneral formula ##STR3## in which

R¹ is methyl or ethyl,

R² is C₁ -C₆ alkyl or alkenyl, C₁ -C₆ alkyl substituted by aryl, phenyl,C₁ -C₆ alkylphenyl, or halophenyl

R³ is C₁ -C₆ alkyl, C₁ -C₆ alkyl substituted by halogen, phenyl, C₁ -C₆alkylphenyl, C₁ -C₆ alkoxyphenyl, halophenyl, or nitrophenyl, and

X is oxygen or sulfur.

It has been found that compounds of the formula (I) exhibit unusuallystrong insecticidal, acaricidal and nematicidal activities, and possessa higher effectiveness and a wider controlling effect than compounds ofthe formula (VIII); particularly, they have an excellent activityagainst spider mites that have attained resistance to various knownorganophosphorus pesticides.

Preferably, in formula (I), R² represents C₁ -C₄ alkyl, an alkenylradical selected from vinyl, allyl, propenyl and methallyl (allyl beingespecially preferred), an arylalkyl group selected from benzyl and2-phenylethyl (benzyl being especially preferred), unsubstituted phenylor a phenyl carrying one to three (especially one or two) substituentsselected from chlorine and C₁ -C₄ alkyl groups (especially methyl), andR³ represents C₁ -C₄ alkyl, halogenated C₁ -C₄ alkyl for (examplebromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-chlorobutyl,4-chlorobutyl, 1-methyl-2-chloropropyl, 1-methyl-3-chloropropyl,1-chloromethyl-ethyl, 1-chloromethyl-2-chloroethyl and, especially,chloromethyl), unsubstituted phenyl or phenyl carrying one to threesubstituents selected from C₁ -C₄ alkyl (especially methyl), halogen(especially chlorine and bromine), C₁ -C₄ alkoxy (especially methoxy)and nitro.

The present invention also provides a process for the preparation of acompound of the formula (I) in which (a) a phosphoramidothioate salt ofthe general formula ##STR4## in which

R¹, R² and R³ have the meanings stated above, and

M¹ is an alkali metal atom or an ammonium group, is reacted with analkylating agent of the general formula

    CH.sub.3 CH.sub.2 CH.sub.2.Y                               (III),

in which

Y is a halogen atom or a sulfonic acid group, or (b) a thio (or dithio)phosphoryl halide of the general formula ##STR5## in which

R¹ and X have the meanings stated in claim 1 and

Hal is halogen,

is reacted with a sulfonamide salt of the general formula ##STR6## inwhich

R² and R³ have the meanings stated in claim 1 and

M² is an alkali metal atom.

The phosphoramidothioate salt (II) to be used in process variant (a) canbe prepared by reacting a phosphoramidothioate of the general formula##STR7## in which

R¹, R² and R³ have the meanings stated in claim 1, with a dealkylatingagent of the general formula

    R.sup.4 SM.sup.1                                           (VII),

in which

M¹ has the meaning given above, and

R⁴ is hydrogen, alkyl or alkoxythiocarbonyl.

Preferably, in the above formulas (II), (III) and (VII), M¹ represents asodium or potassium atom, or an ammonium group; Y represents chlorine,bromine, iodine, fluorine, benzenesulfonate, p-toluenesulfonate,monopropylsulfonate or sulfate; and R⁴ represents hydrogen, a C₁ -C₄alkyl group, methoxythiocarbonyl or ethoxythiocarbonyl.

Specific examples of the phosphoramidothioate salts of the formula (II)are as follows: potassiumO-ethyl-N-methyl-N-methanesulfonylphosphoramidothioate, potassiumO-ethyl-N-methyl-N-ethanesulfonylphosphoramidothioate, potassiumO-ethyl-N-methyl-N-n-butanesulfonylphosphoramidothioate, potassiumO-methyl-N-methyl-N-benzenesulfonylphosphoramidothioate, potassiumO-ethyl-N-methyl-N-benzenesulfonylphosphoramidothioate, potassiumO-ethyl-N-methyl-N-4-chlorobenzenesulfonylphosphoramidothioate,potassiumO-ethyl-N-methyl-N-2,5-dichlorobenzenesulfonylphosphoramidothioate,potassiumO-ethyl-N-methyl-N-4-methylbenzenesulfonylphosphoramidothioate,potassiumO-ethyl-N-methyl-N-4-methoxybenzenesulfonylphosphoramidothioate,potassiumO-ethyl-N-methyl-N-2-methoxy-5-chlorobenzenesulfonylphosphoramidothioate,potassium O-ethyl-N-methyl-N-2-nitrobenzenesulfonylphosphoramidothioate,potassium O-ethyl-N-ethyl-N-methanesulfonylphosphoramidothioate,potassium O-ethyl-N-iso-propyl-N-methanesulfonylphosphoramidothioate,potassiumO-ethyl-N-iso-propyl-N-chloromethanesulfonylphosphoramidothioate,potassium O-ethyl-N-iso-propyl-N-benzenesulfonylphosphoramidothioate,potassium O-ethyl-N-n-butyl-N-methanesulfonylphosphoramidothioate,potassium O-ethyl-N-allyl-N-methanesulfonylphosphoramidothioate,potassium O-ethyl-N-allyl-N-benzenesulfonylphosphoramidothioate,potassium O-ethyl-N-phenyl-N-methanesulfonylphosphoramidothioate,potassium O-ethyl-N-phenyl-N-benzenesulfonylphosphoramidothioate,potassiumO-ethyl-N-4-chlorophenyl-N-methanesulfonylphosphoramidothioate,potassiumO-ethyl-N-4-methylphenyl-N-methanesulfonylphosphoramidothioate,potassiumO-ethyl-N-(2-methyl-4-chlorophenyl)-N-methanesulfonylphosphoramidothioate,potassium O-ethyl-N-benzyl-N-methanesulfonylphosphoramidothioate,potassium O-methyl-N-methyl-N-methanesulfonylphosphoramidothioate,potassiumO-ethyl-N-2-methylphenyl-N-methanesulfonylphosphoramidothioate,potassiumO-ethyl-N-2,4-dimethylphenyl-N-methanesulfonylphosphoramidothioate,potassiumO-ethyl-N-2,4-dichlorophenyl-N-methanesulfonylphosphoramidothioate,potassiumO-ethyl-N-(2-methyl-4-chlorophenyl)-N-benzenesulfonylphosphoramidothioate,potassium O-ethyl-N-methyl-N-chloromethanesulfonylphosphoramidothioate,potassium O-ethyl-N-methyl-N-4-bromobenzenesulfonylphosporamidothioate,and potassiumO-ethyl-N-methyl-N-2,4,5-trichlorobenzenesulfonylphosphoramidothioate,as well as the corresponding sodium salts, triethylammonium salts,dimethylanilinium salts and pyridinium salts.

Specific examples of the alkylating agents of the formula (III) are asfollows: n-propylchloride, n-propyl bromide, n-propyl benzene sulfonate,n-propyl-p-toluene sulfonate, di-n-propyl sulfate, and mono-n-propylsulfate.

Examples of the phosphoramidothioates of the formula (VI) are asfollows: O,O-di-ethyl-N-methyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-ethanesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-n-butanesulfonylphosphoramidothioate,O,O-di-methyl-N-methyl-N-benzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-benzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-4-chlorobenzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-2,5-dichlorobenzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-4-methylbenzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-4-methoxybenzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-2-methoxy-5-chlorobenzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-2-nitrobenzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-ethyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-iso-propyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-iso-propyl-N-chloromethanesulfonylphosphoramidothioate,O,O-di-ethyl-N-iso-propyl-N-benzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-n-butyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-allyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-allyl-N-benzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-phenyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-phenyl-N-benzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-4-chlorophenyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-4-methylphenyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-(2-methyl-4-chlorophenyl)-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-benzyl-N-methanesulfonylphosphoramidothioate,O,O-di-methyl-N-methyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-2-methylphenyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-2,4-dimethylphenyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-2,4-dichlorophenyl-N-methanesulfonylphosphoramidothioate,O,O-di-ethyl-N-(2-methyl-4-chlorophenyl)-N-benzenesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-chloromethanesulfonylphosphoramidothioate,O,O-di-ethyl-N-methyl-N-4-bromobenzenesulfonylphosphoramidothioate, andO,O-di-ethyl-N-methyl-N-2,4,5-trichlorobenzenesulfonylphosphoramidothioate.

Examples of the dealkylating agents of the formula (VII) are as follows:sodium hydrosulfide, potassium hydrosulfide, sodium methanethiolate,potassium ethanethiolate, sodium 2-propanethiolate, potassiummethylxanthogenate, potassium ethylxanthogenate, and ammonium sulfide.

The process variant (a) is illustrated by the following reaction scheme:##STR8##

In the above sequence, the potassiumO-ethyl-N-methyl-N-methanesulfonylphosphoramidothioate obtained in thefirst step may be isolated. However, it is also possible to react it insitu, i.e. without isolation, with the alkylating agent to obtain thedesiredO-ethyl-S-n-propyl-N-methyl-N-methanesulfonylphosphoramidothioate of ahigh purity and in a high yield.

The process variant (a) of the present invention is carried outpreferably using a solvent or diluent. Examples of such solvents ordiluents are water and inert organic solvents selected from aliphatic,alicyclic and aromatic hydrocarbons which optionally may be chlorinated,such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene,xylene, methylene chloride, chloroform, carbon tetrachloride, ethylenechloride, trichloroethylene and chlorobenzene; ethers, such as diethylether, methylethyl ether, diisopropyl ether, dibutyl ether, propyleneoxide, dioxane and tetrahydrofuran; ketones, such as acetone, methylethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone;nitriles, such as acetonitrile, propionitrile and acrylonitrile;alcohols, such as methanol, ethanol, isopropanol, tert.-butanol andethylene glycol; esters, such as ethyl acetate and amyl acetate; acidamides, such as dimethylformamide; sulfones and sulfoxides, such asdimethyl sulfoxide and dimethyl sulfone; and bases, such as pyridine.

The process variant (a) of the present invention can be performed in awide temperature range. In general, the process is carried out at atemperature between -20° C. and the boiling point of the mixture,preferably at a temperature of from 0° to 100° C. Furthermore, thereaction is carried out preferably at atmospheric pressure, although itcan also be performed under an elevated or reduced pressure.

Referring now to process variant (b), in the general formulas (IV) and(V), Hal preferably represents a chlorine atom; and M² preferablyrepresents potassium or sodium.

Specific examples of the thio(or dithio)phosphoryl halides of theformula (IV) are as follows: O-methyl-S-n-propylthiophosphoryl chloride,O-ethyl-S-n-propylthiophosphoryl chloride,O-methyl-S-n-propyldithiophosphoryl chloride, andO-ethyl-S-n-propyldithiophosphoryl chloride.

Specific examples of the sulfonamide salts of the formula (V) are asfollows: sodium N-methylmethanesulfonamide, sodiumN-methylethanesulfonamide, sodium N-methyl-n-butanesulfonamide, sodiumN-methylbenzenesulfonamide, sodium N-methyl-4-chlorobenzenesulfonamide,sodium N-methyl-2,5-dichlorobenzenesulfonamide, sodiumN-methyl-4-methylbenzenesulfonamide, sodiumN-methyl-4-methoxybenzenesulfonamide, sodiumN-methyl-2-methoxy-5-chlorobenzenesulfonamide, sodiumN-methyl-2-nitrobenzenesulfonamide, sodium N-ethylmethanesulfonamide,sodium N-iso-propylmethanesulfonamide, sodiumN-isopropylchloromethanesulfonamide, sodiumN-iso-propylbenzenesulfonamide, sodium N-n-butylmethanesulfonamide,sodium N-allylmethanesulfonamide, sodium N-allylbenzenesulfonamide,sodium methanesulfonanilide, sodium benzenesulfonanilide, sodiummethanesulfone-4-chloroanilide, sodium methanesulfon-4-methylanilide,sodium methanesulfon-2-methyl-4-chloroanilide, sodiumN-benzylmethanesulfonamide, sodium methanesulfon-2-methylanilide, sodiummethanesulfon-2,4-dimethylanilide, sodiummethanesulfon-2,4-dichloroanilide, sodiummethanesulfon-2-methyl-4-chloroanilide, sodiumN-methylchloromethanesulfonamide, sodiumN-methyl-4-bromobenzenesulfonamide, and sodiumN-methyl-2,4,5-trichlorobenzenesulfonamide, and the correspondingpotassium salts.

The process variant (b) is illustrated by the following two reactionschemes: ##STR9##

The carrying out process variant (b) an inert solvent or diluent ispreferably used. The solvents mentioned above in connection with processvariant (a) may be used to obtain the desired product in a high purityand in a high yield.

A wide range of temperature can be employed in process variant (b).Generally, the reaction is effected at a temperature between -20° C. andthe boiling point of the mixture, preferably at from 0° to 100° C.Although it is desirable for the reaction to be carried out atatmospheric pressure, it is also possible to perform the reaction underan elevated or reduced pressure.

As already mentioned, the phosphoric acid ester amides according to theinvention are distinguished by an excellent insecticidal, acaricidal andnematicidal activity. They are active against plant pests, pests harmfulto health and pests of stored products, for example grain, and combine alow phytotoxicity with a good action against both sucking and bitinginsects and against mites; the action sets in quickly and islong-lasting.

For these reasons, the compounds according to the invention can beemployed successfully as pesticides in plant protection and also in thehygiene field and the field of protection of stored products. In thefield of veterinary medicine, the present compounds are effectiveagainst various endoparasites and ectoparasites, such as ticks andinsects.

To the sucking insects there belong, in the main, aphids (Aphididae)such as the green peach aphid (Myzus persicae), the beam aphid (Doralisfabae), the bird cherry aphid (Rhopalsoiphum padi), the pea aphid(Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), thecurrant gall aphid (Cryptomyzus korschelti), the rosy apple aphid(Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and thecherry black-fly (Myzus cerasi); in addition, scales and mealybugs(Coccina), for example the oleander scale (Aspidiotus hederae) and thesoft scale (Lecanium hesperidum) as well as the grape mealybug(Pseudococcus maritimus); thrips (Thysanootera), such as Hercinothripsfemoralis, and bugs, for example the beet bug (Piesma quadrata), the redcotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), theassassin bug (Rhodnius prolixus) and Chagas' bug (Triatoma infestans)and, further, cicadas, such as Euscelis bilobatus and Nephotettixbipunctatus.

In the case of the biting insects, above all there should be mentionedbutterfly and moth caterpillars (Lepidoptera) such as the diamond-backmoth (Plutella maculipennis), the gypsy moth (Lymantria dispar), thebrown-tail moth (Euproctis chrysorrhoea) and tent caterpillar(Malacosoma neustria); further, the cabbage moth (Mamestra brassicae)and the cutworm (Agrotis segetum), the large white butterfly (Pierisbrassicae), the small winter moth (Cheimatobia brumata), the green oaktortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda)and cotton worm (Prodenia litura), the ermine moth (Hyponomeutapaddella), the Mediterranean flour moth (Ephestia kuhniella) and greaterwax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoptera), forexample the granary weevil (Sitophilus granarius = Calandra granaria),the Colorado beetle (Leptinotarsa decemlineata), the dock beetle(Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), theblossom beetle (Meligethes aeneus), the raspberry beetle (Byturustomentosus), the bean weevil (Bruchidius = Acanthoscelides obtectus),the leather beetle (Dermestes frischi), the khapra beetle (Trogodermagranarium), the flour beetle (Tribolium castaneum), the northern cornbillbug (Calandra or Sitophilus zeamais), the drugstore beetle(Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and thesaw-toothed grain beetle (Oryzaephilus surinamensis), and also speciesliving in the soil, for example wireworms (Agriotes spec.) and larvae ofthe cockchafer (Melolontha melolontha); cockroaches, such as the Germancockroach (Blattella germanica), American cockroach (PeriplanetaAmericana), Madeira cockroach (Leucophaea or Rhyparobia maderae),oriental cockroach (Blatta orientalis), the giant cockroach (Blaberusgiganteus) and the black giant cockroach (Blaberus fuscus) as well asHenschoutedenia flexivitta; further, Orthoptera, for example the housecricket (Gryllus domesticus); termites such as the eastern subterraneantermite (Reticulitermes flavipes) and Hymenoptera such as ants, forexample the garden ant (Lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly(Drosophila melanogaster), the Mediterranean fruit fly (Ceratitiscapitata), the house fly (Musca domesticus), the little house fly(Fannia canicularis), the black blow fly (Phormia regina) and bluebottlefly (Calliphora erythrocephala) as well as the stable fly (Stomoxyscalcitrans); further, gnats, for example mosquitoes such as the yellowfever mosquito (Aedes aegypti), the northern house mosquito (Culexpipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acarina) there are classed, in particular, the spidermites (Tetranychidae) such as the two-spotted spider mite (Tetranychusurticae) and the European red mite (Paratetranychus pilosus = Panonychusulmi), gall mites, for example the blackcurrent gall mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithodorus moubata).

When applied against pests harmful to health and pests of storedproducts, particularly flies and mosquitoes, the novel products are alsodistinguished by an outstanding residual activity on wood and clay, aswell as a good stability to alkali on limed substrates.

The active compounds according to the invention couple a low toxicity towarm-blooded animals with powerful nematicidal properties and cantherefore be used to combat nematodes, especially phytopathogenicnematodes. These essentially include leaf nematodes (Arphelenchoides),such as the crysanthemum eel worm (A. ritzemabosi), the leaf blotcheelworm (A. fragariae) and the rice eelworm (A. oryzae); stem netamodes(Ditylenchus), such as the steam eelworm (D. Dipsaci); root-knotnematodes (Meloidogyne), such as M. arenaria and M. incognita;cyst-forming nematodes (Heterodera), such as the potato cyst eelworm (H.rostochiensis) and the beet cyst eelworm (H. schachtii); and alsofree-living root nematodes, for example of the genera Pratylenchus,Paratylenchus, Rotylenchus, Xiphinema and Radopholus.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicles such as gases,solutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: aerosol propellants which are gaseous at normal temperaturesand pressures, such as Freon; inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes,etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleumor mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g.methylene chloride, chloroethylenes, etc.), alcohols, (e.g. methanol,ethanol, propanol, butanol, glycol, etc.) as well as ethers and estersthereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine,etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethylketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; aswell as inert dispersible finely divided solid carriers, such as groundmaterial minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e.calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.)and the ground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates,etc., and especially alkyl arylpolyglycol ethers, magnesium stearate,sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfitewaste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other nematocides,insecticides, acaricides and fungicides, or bactericides, rodenticides,herbicides, fertilizers, growth-regulating agents, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1-95% by weight, andpreferably 0.5-90% by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0001-20%, preferably0.005-10% by weight of the mixture. Thus, the present inventioncontemplates overall compositions which comprise mixtures of aconventional dispersible carrier vehicle such as (1) a dispersible inertfinely divided carrier solid, and/or (2) a dispersible carrier liquidsuch as an inert organic solvent and/or water, preferably including asurface-active effective amount of a carrier vehicle assistant, e.g. asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0.0001-95%, andpreferably 0.0005-95%, by weight of the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to 1000 g/hectare, preferably 40to 600 g/hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound or even the 100% active substance alone, e.g. about 20-100% byweight of the active compound.

When applied to areas of agriculture and particularly when used againstnematodes, the preparations are generally applied in amounts of 1 to 100kg of active compound per hectare, particularly 30 g to 10 kg andespecially 300 g to 6 kg per hectare, and are then incorporated into thesoil.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, acarids andnematodes, which comprises applying to at least one of correspondingly(a) such insects, (b) such acarids, (c) such nematodes and (d) thecorresponding habitat thereof, i.e. the locus to be protected, e.g. to agrowing crop, to an area where a crop is to be grown or to a domesticanimal, a correspondingly combative or toxic amount, i.e. aninsecticidally, acaricidally or nematicidally effective amount, of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, dressing, encrusting, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

Example (i)

A wettable powder was prepared by pulverizing and mixing 15 parts ofcompound No. 6, 80 parts of a mixture (1:5) of diatomaceous earth andkaolin, and 5 parts of an emulsifier RUNNOX (a product of Toho KagakuKogyo Kabushiki Kaisha, polyoxyethylenealkyl phenyl ether). This couldbe diluted with water to 0.05% before application by spraying.

Example (ii)

An emulsifiable concentrate was prepared by mixing and stirring 30 partsof compound No. 2, 30 parts of xylene, 30 parts of KAWAKAZOL(methylnaphthalene, a product of Kawasaki Kasei Chemicals Limited) and10 parts of SORPOL (polyoxyethylene alkylphenyl ether, a product of TohoKagaku Kogyo Kabushiki Kaisha). This could be diluted with water to0.05% before spraying.

Example (iii)

A dusting agent was prepared by pulverizing and mixing 2 parts ofcompound No. 8 and 98 parts of a mixture (1:3) of talc and clay. Thiscould be applied by scattering.

Example (iv)

A dusting agent was prepared by pulverizing and mixing 1.5 parts ofcompound No. 3, 0.5 part of isopropyl hydrogen phosphate (PAP), and 98parts of a mixture (1:3) of talc and clay.

Example (v)

10 parts of compound No. 4, 10 parts of bentonite, 78 parts of a mixture(1:3) of talc and clay, and 2 parts of lignin sulfonate were mixed. 25parts of water were added to the mixture. The whole was mixed thoroughlyand then processed with an extrusion granulator into granules of 20 to40 mesh, which were dried at 40°-50° C.

Example (vi)

95 parts of clay powder having a particle size distribution of 0.2 to 2mm were placed in a rotary mixer. During rotation, there were sprayedover the particles 5 parts of a solution of compound No. 26 in anorganic solvent, thereby wetting them uniformly. Then, drying at 40° to50° C. was effected in order to form granules.

Example (vii)

An oil preparation was prepared by mixing and stirring 0.5 part ofcompound No. 18, 20 parts of VELSICOL AR-50 (high-boiling aromaticcompounds, a product of Velsicol Chem. Co.) and 79.5 parts of kerosine.

The insecticidal, acaricidal and nematicidal activity of the compoundsof this invention is illustrated by the following biotest Examples.

EXAMPLE 1 Test on larvae of Prodenia litura Fabricius

Solvent: xylol, 3 parts by weight

Emulsifier: polyoxyethylene alkylphenylether, 1 part by weight

To form a suitable preparation of the active compound, 1 part by weightof the active compound was mixed with the above amount of the solventcontaining the above amount of the emulsifier, and the mixture wasdiluted with water to a predetermined concentration.

Sweet potato leaves were dipped in an aqueous preparation, of apredetermined concentration, of the active compound. After drying in theair, the leaves were placed in a Petri dish 9 cm in diameter. Then, 10third instar larvae of Prodenia litura Fabricius were placed in thePetri dish. The dish was placed in a constant-temperature room at 28° C.Twenty-four hours later, the number of dead larvae was determined inorder to calculate the kill ratio. The results are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                         Kill ratio (%) at a concentration of (ppm)               Compound No.         1000 300  100  50                                        __________________________________________________________________________     ##STR10##           100  100  100                                             ##STR11##           100  100  100  100                                        ##STR12##           100  100  100  100                                        ##STR13##           100  100  100                                             ##STR14##           100  100  100  100                                        ##STR15##           100  100  100                                             ##STR16##           100  100                                                  ##STR17##           100  100  100                                             ##STR18##           100  100  100                                             ##STR19##           100  100                                                  ##STR20##           100  100  100                                             ##STR21##           100  100  100                                             ##STR22##           100  100  100                                             ##STR23##           100  100  100                                             ##STR24##           100  100  100                                             ##STR25##           100  100  100  100                                        ##STR26##           100  100  100                                             ##STR27##           100  100  100                                             ##STR28##           100  100  100                                             ##STR29##           100  100  100                                             ##STR30##           100  100  100  100                                        ##STR31##           100  100  100  100                                        ##STR32##           100  100                                                  ##STR33##           100  100  100                                             ##STR34##           100  100  100                                             ##STR35##           100  100  100                                             ##STR36##           100  100  100                                             ##STR37##           100  100  100                                             ##STR38##           100  100                                                  ##STR39##           100  100  100                                             ##STR40##           100  100  100                                             ##STR41##           100  100  100                                             ##STR42##           100  100                                                  ##STR43##           100  100  100                                             ##STR44##           100  100  100                                             ##STR45##           100  100  100                                             ##STR46##           100  100  100                                             ##STR47##            0                                                        ##STR48##            0                                                        ##STR49##            0                                                        ##STR50##            30   0                                                   ##STR51##            50   0                                                  __________________________________________________________________________

example 2 test on Nephotettix cincticeps

Rice plants each about 10 cm in height were planted in pots each 12 cmin diameter. On to the rice plants there was applied on aqueouspreparation, at a predetermined concentration, of the active compound(prepared as in Example 1) at a rate of 10 ml per pot. After drying theapplied preparation, wire-gauze cages each 7 cm in diameter and 14 cm inheight were placed over the pots, into which cages 30 female imagos ofNephotettix cincticeps were released. The pots were then placed in aconstant-temperature room and, 24 hours later, the number of deadinsects was determined in order to calculate the kill ratio. The resultsare shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                          Kill ratio (%)                                                                at a concentration of                                       Compound No.        1000    100     50 (ppm)                                  ______________________________________                                         ##STR52##          100     100                                                ##STR53##          100     100                                                ##STR54##          100     100                                                                 Kill ratio (%)                                                                at a concentration of                                       Compound No.        1000    100     (ppm)                                     ______________________________________                                         ##STR55##          100     100                                                ##STR56##          100     100                                                ##STR57##          100     100                                                ##STR58##          100     100                                                ##STR59##          100     100                                                ##STR60##          100     100                                                ##STR61##          100     100                                                ##STR62##          100     100                                                ##STR63##          100     100                                                ##STR64##          100     100                                                ##STR65##          100     100                                                ##STR66##          100     100                                                ##STR67##          100     100                                                ##STR68##          100     100                                                ##STR69##          100     100                                                ##STR70##          100     100                                                ##STR71##          100     100                                                ##STR72##           40      0                                                 ##STR73##           40      0                                                 ##STR74##           50      0                                                 ##STR75##          100      0                                                 ##STR76##          100      0                                                ______________________________________                                    

example 3 test on Callosobruchus chinensis

The bottom of a Petri dish 9 cm in diameter was covered with a filterpaper, onto which was placed 1 ml of an aqueous preparation, at apredetermined concentration, of the active compound (prepared as inExample 1). 20 Callosobruchus chinensis beetles were placed therein, andthe Petri dish was allowed to stand in a constant-temperature room at28° C. for 24 hours. After 24 hours had elapsed, the number of deadbeetles was determined in order to calculate the kill ratio. The resultsare shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                            Kill ratio (%)                                                                at a concentration of                                     Compound No.          1000   100    10 (ppm)                                  ______________________________________                                         ##STR77##            100    100                                               ##STR78##            100    100                                               ##STR79##            100    100                                               ##STR80##            100    100                                               ##STR81##            100    100                                               ##STR82##            100    100                                               ##STR83##            100    100                                               ##STR84##            100    100                                               ##STR85##            100    100                                               ##STR86##            100    100    100                                        ##STR87##            100    100                                               ##STR88##            100    100                                               ##STR89##            100    100                                               ##STR90##            100    100                                               ##STR91##            100    100                                               ##STR92##            100    100                                               ##STR93##            100    100    100                                        ##STR94##            100    100                                               ##STR95##            100    100                                               ##STR96##            100    100                                               ##STR97##            100    100                                               ##STR98##            100    100                                               ##STR99##            100    100                                               ##STR100##           0                                                        ##STR101##           0                                                        ##STR102##           0                                                        ##STR103##           100    0                                                 ##STR104##           100    0                                                ______________________________________                                    

example 4 test on larvae of Culex pipiens pallens Coquillett

100 ml of an aqueous preparation, at a predetermined concentration, ofthe active compound was placed in a high-walled Petri dish 9 cm indiameter. Into the dish were released 25 4th instar larvae of Culexpipiens pallens Coquillett, and then the dish was placed in aconstant-temperature room at 28° C. Twenty-four hours later the numberof dead larvae was determined to calculate the kill ratio. The resultsare shown in Table 4.

                  TABLE 4                                                         ______________________________________                                                              Kill ratio (%) at                                                             a concentration of                                                            active ingredient                                                             (ppm) of                                                Compound No.            1      0.1    0.01                                    ______________________________________                                         ##STR105##             100                                                    ##STR106##             100                                                    ##STR107##             100                                                    ##STR108##             100                                                    ##STR109##             100                                                    ##STR110##             100                                                    ##STR111##             100                                                    ##STR112##             100    100                                             ##STR113##             100    100                                             ##STR114##             100                                                    ##STR115##             100                                                    ##STR116##             100                                                    ##STR117##             100                                                    ##STR118##             100                                                    ##STR119##             100                                                    ##STR120##             100                                                    ##STR121##             100                                                    ##STR122##             100                                                    ##STR123##             100                                                    ##STR124##             100                                                    ##STR125##             100    100                                             ##STR126##             100    100                                             ##STR127##             100    100    100                                      ##STR128##             100                                                    ##STR129##             100                                                    ##STR130##             100                                                    ##STR131##             100                                                    ##STR132##             100    100                                             ##STR133##             100                                                    ##STR134##             100                                                    ##STR135##             100                                                    ##STR136##             100                                                    ##STR137##             100    100    100                                      ##STR138##             0                                                      ##STR139##             0                                                      ##STR140##             0                                                      ##STR141##             0                                                      ##STR142##             0                                                     ______________________________________                                    

example 5 test on Blattella germanica

The bottom of a Petri dish 9 cm in diameter was covered with a filterpaper, onto which was placed 1 ml of an aqueous preparation, at apredetermined concentration, of the active compound (prepared as inExample 1. 10 imagoes of Blattella germanica were placed therein, andthe Petri dish was allowed to stand in a constant-temperature room at28° C. for 24 hours. After 24 hours had elapsed, the number of deadimagoes was determined to calculate the kill ratio. The results areshown in Table 5.

                  TABLE 5                                                         ______________________________________                                                               Kill ratio (%) at                                                            a concentration of                                                            active ingredient                                                             (ppm) of                                                 Compound No.           1000    100                                           ______________________________________                                         ##STR143##             100                                                    ##STR144##             100                                                    ##STR145##             100                                                    ##STR146##             100                                                    ##STR147##             100                                                    ##STR148##             100                                                    ##STR149##             100                                                    ##STR150##             100                                                    ##STR151##             100                                                    ##STR152##             100                                                    ##STR153##             100                                                    ##STR154##             100                                                    ##STR155##             100                                                    ##STR156##             100     100                                            ##STR157##             100     100                                            ##STR158##             100                                                    ##STR159##             100                                                    ##STR160##             100                                                    ##STR161##             100                                                    ##STR162##             100     100                                            ##STR163##             100                                                    ##STR164##             100                                                    ##STR165##             100                                                    ##STR166##             100                                                    ##STR167##             100                                                    ##STR168##             100                                                    ##STR169##              0                                                     ##STR170##              0                                                     ##STR171##              0                                                     ##STR172##              0                                                     ##STR173##              0                                                    ______________________________________                                          pg,46

example 6 test on Musca domestica vicina

A filter paper was laid on the bottom of a Petri dish 9 cm in diameter,and 1 ml of an aqueous preparation, at a predetermined concentration, ofthe active compound (prepared as in Example 1) was put into the dish. 10female imagos of Musca domestica vicina were introduced therein. Then,the dish was placed in a constant-temperature room at 28° C., and 24hours later, the number of killed imagos was determined in order tocalculate the kill ratio. The results are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                                              Kill ratio (%)                                                                at a concen-                                                                  tration of active                                                             ingredient (ppm)                                                              of                                                      Compound No.            1000     100                                          ______________________________________                                         ##STR174##             100                                                   (1)                                                                            ##STR175##             100      100                                          (2)                                                                            ##STR176##             100      100                                          (3)                                                                            ##STR177##             100                                                   (4)                                                                            ##STR178##             100      100                                          (5)                                                                            ##STR179##             100                                                   (6)                                                                            ##STR180##             100                                                   (7)                                                                            ##STR181##             100      100                                          (8)                                                                            ##STR182##             100                                                   (10)                                                                           ##STR183##             100                                                   (12)                                                                           ##STR184##             100      100                                          (13)                                                                           ##STR185##             100                                                   (14)                                                                           ##STR186##             100                                                   (15)                                                                           ##STR187##             100                                                   (16)                                                                           ##STR188##             100      100                                          (17)                                                                           ##STR189##             100      100                                          (18)                                                                           ##STR190##             100      100                                          (19)                                                                           ##STR191##             100                                                   (20)                                                                           ##STR192##             100      100                                          (21)                                                                           ##STR193##             100                                                   (22)                                                                           ##STR194##             100                                                   (23)                                                                           ##STR195##             100      100                                          (24)                                                                           ##STR196##             100      100                                          (25)                                                                           ##STR197##             100      100                                          (26)                                                                           ##STR198##             100                                                   (27)                                                                           ##STR199##             100      100                                          (28)                                                                           ##STR200##             100      100                                          (29)                                                                           ##STR201##             100      100                                          (30)                                                                           ##STR202##             100                                                   (31)                                                                           ##STR203##             100      100                                          (32)                                                                           ##STR204##             100      100                                          (33)                                                                           ##STR205##             100                                                   (34)                                                                           ##STR206##             100                                                   (35)                                                                           ##STR207##             100                                                   (36)                                                                           ##STR208##             100                                                   (40)                                                                           ##STR209##             100                                                   (41)                                                                           ##STR210##              0                                                    (A)                                                                            ##STR211##              0                                                    (B)                                                                            ##STR212##              0                                                    (C)                                                                           ______________________________________                                    

example 7 test on the two-spotted spider mite, Tetranychus telarius(spray test)

The leaves of kidney bean plants in the two-leaf stage were infestedwith 50 to 100 imagos of Tetranychus telarius (a resistant strain withrespect to organophosphorus compounds). The kidney bean plants werecultivated in pots each 9 cm in diameter. Two days after theinfestation, an aqueous preparation, at a predetermined concentration,of the active compound (formulated as in Example 1) was sprayed over theleaves at a rate of 20 ml per pot. Then, the pots were put in agreenhouse. 10 days later, the acaricidal effect was evaluated andexpressed on the following scale:

3 -- 0% survival of the spider mites

2 -- not more than 5% survival based on an untreated control

1 -- 6-50% survival based on an untreated control

0 -- more than 51% survival based on an untreated control

The results are shown in Table 7.

                                      TABLE 7                                     __________________________________________________________________________                          Kill ratio (%) in a concentration of                                          active ingredient (ppm) of                              Compound No.          1000                                                                              300 100 50  10                                      __________________________________________________________________________     ##STR213##           3   3   3   3                                           (1)                                                                            ##STR214##           3   3   3   3   2                                       (2)                                                                            ##STR215##           3   3   3   3                                           (3)                                                                            ##STR216##           3   3   3                                               (4)                                                                            ##STR217##           3   3   2                                               (5)                                                                            ##STR218##           3   3   3   3                                           (6)                                                                            ##STR219##           3   3   3   3                                           (7)                                                                            ##STR220##           3   3   3   3   3                                       (8)                                                                            ##STR221##           3   3                                                   (9)                                                                            ##STR222##           3   3                                                   (10)                                                                           ##STR223##           3   3   3   2                                           (11)                                                                           ##STR224##           3   3   3   3   3                                       (12)                                                                           ##STR225##           3   3   2                                               (13)                                                                           ##STR226##           3   3   3   3                                           (14)                                                                           ##STR227##           3   3   3   3                                           (15)                                                                           ##STR228##           3   3   3                                               (16)                                                                           ##STR229##           3   3   3   3                                           (17)                                                                           ##STR230##           3   3   3                                               (18)                                                                           ##STR231##           3   3   3                                               (19)                                                                           ##STR232##           3   3   3   3                                           (20)                                                                           ##STR233##           3   3   3   3                                           (21)                                                                           ##STR234##           3   3   3   3   3                                       (22)                                                                           ##STR235##           3   3   3   3   3                                       (23)                                                                           ##STR236##           3   3   3   3   2                                       (24)                                                                           ##STR237##           3   3   3                                               (25)                                                                           ##STR238##           3   3   3                                               (26)                                                                           ##STR239##           3   3   2                                               (27)                                                                           ##STR240##           3   3                                                   (28)                                                                           ##STR241##           3   3                                                   (29)                                                                           ##STR242##           3   3   3   2                                           (30)                                                                           ##STR243##           3   3   3                                               (31)                                                                           ##STR244##           3   3   2                                               (32)                                                                           ##STR245##           3   3                                                   (33)                                                                           ##STR246##           3   3                                                   (34)                                                                           ##STR247##           3   3   3                                               (35)                                                                           ##STR248##           3   3   3                                               (36)                                                                           ##STR249##           3   3   3                                               (37)                                                                           ##STR250##           3   3   3                                               (38)                                                                           ##STR251##           3   3   3                                               (39)                                                                           ##STR252##           3   3   3                                               (40)                                                                           ##STR253##           3   3   3                                               (41)                                                                           ##STR254##           3   3   3                                               (42)                                                                           ##STR255##           0                                                       (A)                                                                            ##STR256##           0                                                       (B)                                                                            ##STR257##           0                                                       (C)                                                                            ##STR258##           0                                                       (D)                                                                            ##STR259##           0                                                       (E)                                                                           __________________________________________________________________________

example 8

test on the two-spotted spider mite, Tetranychus telarius (irrigationtest)

The leaves of kidney bean plants in the two-leaf stage were infestedwith 50 to 100 imagos of Tetranychus telarius (a resistant strain withrespect to organophosphorus compounds).

Two days later, an aqueous preparation, at a predeterminedconcentration, of the active compound (formulated as in Example 1) wasfed, by irrigation, to the roots of the kidney bean plants at a rate of20 ml per pot. Then, the pots were placed in a greenhouse, and 10 dayslater, the acaricidal effect was evaluated and expressed on thefollowing scale:

3 -- 0% survival of the spider mites

2 -- not more than 5% survival based on an untreated control

1 -- 6-50% survival based on an untreated control

0 -- more than 51% survival based on an untreated control

The results are shown in Table 8.

                                      TABLE 8                                     __________________________________________________________________________                          Kill ratio (%) in a concentration of                                          active ingredient (ppm) of                              Compound No.          1000                                                                              300 100 50  10                                      __________________________________________________________________________     ##STR260##           3                                                       (1)                                                                            ##STR261##           3   3   3   3   3                                       (2)                                                                            ##STR262##           3   3   3                                               (3)                                                                            ##STR263##           3   3   3                                               (4)                                                                            ##STR264##           3   3                                                   (5)                                                                            ##STR265##           3   2                                                   (6)                                                                            ##STR266##           3                                                       (7)                                                                            ##STR267##           3                                                       (8)                                                                            ##STR268##           3   3   3                                               (13)                                                                           ##STR269##           3   3   3                                               (14)                                                                           ##STR270##           3   3   2                                               (15)                                                                           ##STR271##           3   3   3                                               (17)                                                                           ##STR272##           3   3   3                                               (18)                                                                           ##STR273##           3   3                                                   (21)                                                                           ##STR274##           3   3                                                   (22)                                                                           ##STR275##           3   3                                                   (23)                                                                           ##STR276##           3   2                                                   (24)                                                                           ##STR277##           3   3   3                                               (25)                                                                           ##STR278##           3   3   3                                               (26)                                                                           ##STR279##           3                                                       (30)                                                                           ##STR280##           3                                                       (31)                                                                           ##STR281##           3                                                       (32)                                                                           ##STR282##           3   3   3                                               (35)                                                                           ##STR283##           3                                                       (36)                                                                           ##STR284##           3   3   3                                               (40)                                                                           ##STR285##           0                                                        (A)                                                                           ##STR286##           0                                                       (B)                                                                            ##STR287##           0                                                       (C)                                                                            ##STR288##           0                                                       (D)                                                                            ##STR289##           0                                                       (E)                                                                           __________________________________________________________________________

example 9 test on Melodogyne incognita acrita

An active-compound preparation was prepared by pulverizing and mixing 2parts by weight of the active compound and 98 parts by weight of talc.

The active compound processed as above was added to soil infested byMeloidogyne incognita acrita in such amounts as to give a concentrationof 50 ppm, 25 ppm, 10 ppm and 5 ppm, respectively. The mixture wasstirred and mixed uniformly and then charged into pots each of 0.0002are. In the treated soil were sown about 20 seeds of tomato (variety:KURIHARA) per pot. The tomato seeds were cultivated in a greenhouse.Four weeks later, the grown roots were withdrawn without damaging them,and the degree of injury of 10 roots out of them was evaluated based onthe following ratings to determine a rootknot index:

Degree of Injury

0 -- no root-knot formation (perfect control)

1 -- slight root-knot formation

3 -- much root-knot formation

4 -- most root-knot formation (corresponding to non-treatment) ##EQU1##

A control effect of 100% means perfect control. The results are shown inTable 9.

                                      TABLE 9                                     __________________________________________________________________________                           Control effect (%) at a concen-                                               tration of active ingredient                                                  (ppm) of                                               Compound No.           50  25  10  5                                          __________________________________________________________________________     ##STR290##            100 100                                                (1)                                                                            ##STR291##            100 100 100 100                                        (2)                                                                            ##STR292##            100 100 100 100                                        (3)                                                                            ##STR293##            100 100 100 100                                        (4)                                                                            ##STR294##            100 100 100 100                                        (5)                                                                            ##STR295##            100 88.0                                               (6)                                                                            ##STR296##            100 100 100 100                                        (7)                                                                            ##STR297##            100 100                                                (8)                                                                            ##STR298##            100                                                    (9)                                                                            ##STR299##            100                                                    (10)                                                                           ##STR300##            100 100                                                (11)                                                                           ##STR301##            100 100                                                (12)                                                                           ##STR302##            100 100 100 100                                        (13)                                                                           ##STR303##            100 100                                                (14)                                                                           ##STR304##            100 100 93.2                                           (15)                                                                           ##STR305##            100                                                    (16)                                                                           ##STR306##            100 100 100                                            (17)                                                                           ##STR307##            100 100 100 100                                        (18)                                                                           ##STR308##            100 95.0                                               (19)                                                                           ##STR309##            100 100 100 82.5                                       (20)                                                                           ##STR310##            100 100 100 88.3                                       (21)                                                                           ##STR311##            100 100                                                (22)                                                                           ##STR312##            100 100 100 83.6                                       (23)                                                                           ##STR313##            100 100 100                                            (24)                                                                           ##STR314##            100 100 92.9                                           (25)                                                                           ##STR315##            100 100                                                (26)                                                                           ##STR316##            100                                                    (27)                                                                           ##STR317##            100                                                    (28)                                                                           ##STR318##            100                                                    (29)                                                                           ##STR319##            100 100 95.0                                           (30)                                                                           ##STR320##            100 100                                                (31)                                                                           ##STR321##            100 89.1                                               (32)                                                                           ##STR322##            100                                                    (33)                                                                           ##STR323##            100 97.5                                               (34)                                                                           ##STR324##            100 100 100 100                                        (35)                                                                           ##STR325##            100 100 100 100                                        (36)                                                                           ##STR326##            100 74.7                                               (37)                                                                           ##STR327##            100 70.7                                               (38)                                                                           ##STR328##            100 100 70.0                                           (39)                                                                           ##STR329##            100 100 100 100                                        (40)                                                                           ##STR330##            100 100 64.3                                           (41)                                                                           ##STR331##            100 100 74.0                                           (42)                                                                           ##STR332##            0                                                      (A)                                                                            ##STR333##            0                                                      (B)                                                                            ##STR334##            0                                                      (C)                                                                            ##STR335##            22.3                                                   (D)                                                                            ##STR336##            22.3                                                   (E)                                                                           __________________________________________________________________________

the following preparative Examples illustrate the process for preparingthe compounds of the present invention:

EXAMPLE 10 ##STR337##

37 g of potassiumO-ethyl-N-methyl-N-4-chlorobenzenesulfonylphosphoramidothioate wasdissolved in 150 ml of methyl ethyl ketone, and 14 g of n-propyl bromidewas added. The mixture was heated at 60°-70° C. for 3 hours to completethe reaction. After distilling off the methyl ethyl ketone, toluene wasadded to the residue, and the mixture was washed with water, with 1%aqueous sodium hydroxide and again with water. After distilling off thetoluene under reduced pressure, 31 g ofO-ethyl-S-n-propyl-N-methyl-N-4-chlorobenzenesulfonylphosphoramidothiolatewas obtained as a colorless oil (n_(D) ²⁰ = 1.5335).

EXAMPLE 11 ##STR338##

5.6 g of potassium hydroxide was dissolved in 100 ml of ethanol, and thesolution was saturated with gaseous hydrogen sulfide at room temperatureto form an ethanol solution of potassium hydrosulfide. 26 g ofO,O-diethyl-N-methyl-N-methane sulfonylphosphoramidothioate was added tothis solution, and the mixture was stirred at 75°-80° C. for 4 hours.The internal temperature was cooled to about 40° C., and then 14 g ofn-propyl bromide was added, followed by stirring at 65° C. for 3 hoursto complete the reaction.

The volatile components were removed from the reaction mixture underreduced pressure, toluene was added to the residue, and the mixture waswashed with water, with 1% aqueous sodium hydroxide and again withwater. After drying the mixture over anhydrous sodium sulfate, toluenewas removed to obtain 22 g ofO-ethyl-S-n-propyl-N-methyl-N-methanesulfonylphosphoramidothiolate as acolorless oil (n_(D) ²⁰ = 1.5020).

EXAMPLE 12 ##STR339##

21 g of sodium methanesulfonanilide was suspended in 150 ml of toluene,and 20 g of O-ethyl-S-n-propylthiophosphoryl chloride was added. Themixture was heated at 80°-90° C. for 3 to 4 hours to complete thereaction. After the reaction had ceased, the reaction mixture was cooledto room temperature and washed with water, with a 1% aqueous solution ofsodium hydroxide, and again with water. The mixture was then dried overanhydrous sodium sulfate.

Toluene was distilled from the dried reaction mixture under reducedpressure to obtain 25 g ofO-ethyl-S-n-propyl-N-phenyl-N-methanesulfonylphosphoramidothiolate as acolorless oil (n_(D) ²⁰ = 1.5400).

The following compounds were prepared by procedures analogous to thoseof the preceding Examples.

                  Table 10                                                        ______________________________________                                         ##STR340##                                                                   Com-                                                                          pound                                Physical                                 No.   R.sup.1                                                                              R.sup.2      R.sup.3    constants                                ______________________________________                                        4     C.sub.2 H.sub.5                                                                      CH.sub.3     C.sub.2 H.sub.5                                                                          n.sub.D.sup.20 1.4985                    5     C.sub.2 H.sub.5                                                                      CH.sub.3     n-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.4952                    6     CH.sub.3                                                                             CH.sub.3                                                                                    ##STR341##                                                                              n.sub.D.sup.20 1.5245                    7     C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR342##                                                                              n.sub.D.sup.20 1.5190                    8     C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR343##                                                                              n.sub.D.sup.20 1.5394                    9     C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR344##                                                                              n.sub.D.sup.20 1.5350                    10    C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR345##                                                                              n.sub.D.sup.20  1.5456                   11    C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR346##                                                                              n.sub.D.sup.20 1.5572                    12    C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR347##                                                                              n.sub.D.sup.20 1.5420                    13    C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                            CH.sub.3   n.sub.D.sup.20  1.4972                   14    C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                          CH.sub.3   n.sub.D.sup.20 1.5010                    15    C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                          CH.sub.2 Cl                                                                              n.sub.D.sup.20 1.5009                    16    C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                           ##STR348##                                                                              n.sub.D.sup.20 1.5337                    17    C.sub.2 H.sub.5                                                                      n-C.sub.4 H.sub.9                                                                          CH.sub.3   n.sub.D.sup.20 1.4898                    18    C.sub.2 H.sub.5                                                                      CH.sub.2 CHCH.sub.2                                                                        CH.sub.3   n.sub.D.sup.20 1.5038                    19    C.sub.2 H.sub.5                                                                      CH.sub.2 CHCH.sub.2                                                                         ##STR349##                                                                              n.sub.D.sup.20 1.5404                    20    C.sub.2 H.sub.5                                                                       ##STR350##                                                                                 ##STR351##                                                                              n.sub.D .sup.20 1.5550                   21    C.sub.2 H.sub.5                                                                       ##STR352##  CH.sub.3   n.sub.D.sup.20 1.5371                    22    C.sub.2 H.sub.5                                                                       ##STR353##  CH.sub.3   n.sub.D.sup.20 1.5367                    23    C.sub.2 H.sub.5                                                                       ##STR354##  CH.sub.3   n.sub.D.sup.20 1.5380                    24    C.sub.2 H.sub.5                                                                       ##STR355##  CH.sub.3   n.sub.D.sup.20 1.5444                    35    CH.sub.3                                                                             CH.sub.3     CH.sub.3   n.sub.D.sup.20 1.5030                    36    C.sub.2 H.sub.5                                                                       ##STR356##  CH.sub.3   n.sub.D.sup.20 1.5359                    37    C.sub.2 H.sub.5                                                                       ##STR357##  CH.sub.3   n.sub.D.sup.20 1.5300                    38    C.sub.2 H.sub.5                                                                       ##STR358##  CH.sub.3   n.sub.D.sup.20 1.5390                    39    C.sub.2 H.sub.5                                                                       ##STR359##                                                                                 ##STR360##                                                                              n.sub.D.sup.20 1.5429                    40    C.sub.2 H.sub.5                                                                      CH.sub.3     CH.sub.2 Cl                                                                              n.sub.D.sup.20 1.5075                    41    C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR361##                                                                              n.sub.D.sup.20 1.5532                    42    C.sub.2 H.sub.5                                                                      CH.sub.3                                                                                    ##STR362##                                                                              m.p. 99-101                              ______________________________________                                    

EXAMPLE 13 ##STR363##

13.1 g of sodium N-methylmethanesulfonamide was suspended in 100 ml ofacetonitrile. 21.9 g of O-ethyl-S-n-propyldithiophosphoryl chloride wasadded at room temperature and, after gradual heating, the mixture wasstirred at 40°-50° C. for 4 hours. After completion of the reaction,acetonitrile was distilled off, toluene was added to the residue, andthe mixture was washed with water, with a 1% aqueous solution of sodiumhydroxide and again with water. After drying the toluene layer overanhydrous sodium sulfate, toluene was removed at reduced pressure,followed by drying for another hour at 70° C./1 mm Hg to obtain 22 g ofO-ethyl-S-n-propyl-N-methyl-N-methane sulfonylphosphoramidodithioate asa colorless oil (n_(D) ²⁰ 1.5295).

The following compounds were prepared by methods analogous to those ofthe preceding Examples.

                  Table 11                                                        ______________________________________                                         ##STR364##                                                                   Com-                                                                          pound                               Physical                                  No.   R.sup.1 R.sup.2      R.sup.3  constants                                 ______________________________________                                        26    C.sub.2 H.sub.5                                                                       CH.sub.3     C.sub.2 H.sub.5                                                                        n.sub.D.sup.20 1.5214                     27    C.sub.2 H.sub.5                                                                       CH.sub.3                                                                                    ##STR365##                                                                            n.sub.D.sup.20 1.5440                     28    C.sub.2 H.sub.5                                                                       CH.sub.3                                                                                    ##STR366##                                                                            n.sub.D.sup.20 1.5535                     29    C.sub.2 H.sub.5                                                                       CH.sub.3                                                                                    ##STR367##                                                                            n.sub.D.sup.20 1.5735                     30    C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                            CH.sub.3 n.sub.D.sup.20 1.5220                     31    C.sub.2 H.sub.5                                                                       i-C.sub.3 H.sub.7                                                                          CH.sub.3 n.sub.D.sup.20 1.5060                     32    C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                        CH.sub.3 n.sub.D.sup.20 1.5245                     33    C.sub.2 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                         ##STR368##                                                                            n.sub.D.sup.20 1.5410                     34    C.sub.2 H.sub.5                                                                        ##STR369##  CH.sub.3 n.sub.D.sup.20 1.5530                     ______________________________________                                    

other compounds of formula I which can be similarly prepared include:

                                      TABLE 12                                    __________________________________________________________________________    Com-                                                                          pound                                                                         No.   R.sup.1                                                                           R.sup.2       R.sup.3      X                                        __________________________________________________________________________    43    CH.sub.3                                                                           ##STR370##                                                                                  ##STR371##  0                                        44    C.sub.2 H.sub.5                                                                    ##STR372##   CH.sub.2CH.sub.2CH.sub.2Br                                                                 0                                        45    CH.sub.3                                                                           ##STR373##                                                                                  ##STR374##  0                                        __________________________________________________________________________

and the like.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. An O-alkyl-S-n-propyl-N-sulfonyl-phosphoric acidester amide of the formula ##STR375## in which R¹ is methyl or ethyl,R²is C₁ -C₆ alkyl or alkenyl, C₁ -C₆ alkyl substituted by aryl, phenyl, C₁-C₆ alkylphenyl, or halophenyl, and R³ is C₁ -C₆ alkyl, C₁ -C₆ alkylsubstituted by halogen, phenyl, C₁ -C₆ alkylphenyl, C₁ -C₆ alkoxyphenyl,halophenyl, or nitrophenyl.
 2. A method of combating insects, acarids ornematodes, which comprises applying to the insects, acarids, ornematodes, or to a habitat thereof an insecticidally, acaricidally ornematicidally effective amount of a compound according to claim
 1. 3. Acompound according to claim 1, in which R² is alkyl having 1 to 4 carbonatoms, allyl, benzyl, phenyl or phenyl carrying one or two substituentsselected from chlorine and methyl, and R³ is alkyl having 1 to 4 carbonatoms, chloromethyl, phenyl or phenyl carrying one to three substituentsselected from chlorine, bromine, methyl, methoxy and nitro.
 4. Thecompound according to claim 1, wherein such compound isO-ethyl-S-n-propyl-N-methyl-N-methanesulfonylphosphoramidodithioate ofthe formula ##STR376##
 5. An insecticidal, acaricidal or nematicidalcomposition containing as active ingredient an insecticidally,acaricidally or nematicidally effective amount of a compound accordingto claim 1 in admixture with a diluent.
 6. The method according to claim2, in which said compoundisO-ethyl-S-n-propyl-N-methyl-N-methanesulfonylphosphoramidodithioate.